Acaricidal compositions containing an o-(2-alkyl-4,6-dinitro-phenyl)-o&#39;-(alpha-carbalkoxy-alkyl)-carbonate

ABSTRACT

WHEREIN R IS STRANGTH OR BRABCHED ALKYL OF 1 TO 12 CARBON ATOMS, R&#39;&#39; IS STRANGHT OR BRANCHED ALKYL OF 1 TO 8 CARBN ATOMS OR CYCLOHEXYL, AND N IS 0 TO 1.   ACARICIDAL COMPOSITIONS CONTAINING AS AN ACTIVE ACARICIDAL INGREDIENT A COMPOUND OF THE FORMULA 1,3-DI(O2N-),5-R&#39;&#39;,6-(R-OOC-(CH2)N-CH(-CH3)-O-CO-O-)BENZENE

United States Patent ABSTRACT OF THE DISCLOSURE Acaricidal compositions containing as an active acaricidal ingredient a compound of the formula Ha N 03 wherein R is straight or branched alkyl of 1 to 12 carbon atoms, R is straight or branched alkyl of 1 to -8 carbon atoms or cyclohexyl, and

nisOto 1.

OzN R wherein m R is straight or branched alkyl of l to 12 carbon atoms, R is straight or branched alkyl of 1 to 8 carbon atoms or cyclohexyl, and n is 0 or 1.

A compound of the Formula I is prepared by either of the following methods;

METHOD A By reacting a 2-alkyl-4,G-dinitro-phenol compound of the formula OiN R wherein R has the same meanings as in Formula I, and A is hydrogen or an alkali metal,

with phosgene to form a chlorocarbonate of the formula OzN E NO: (11a) where R has the same meanings as in Formula I and 0 reacting the intermediate IIa with a hydroxy-alkanoic acid ester of the formula HO-flJH-(CHzh-COOR CH3 (III) wherein R and n have the same meanings as in Formula I.

METHOD B By reacting a hydroxy-alkanoic acid ester compound of the formula CH3 (IV) wherein R and n have the same meanings as in Formula I, and A has the same meanings as in Formula II,

with phosgene to form a chlorocarbonate of the formula Cl-(l-O-(fH-(CHzM-COOR 0H3 (IVa) where R and n have the same meanings as in Formula I, and reacting the intermediate IVa with a 2-alkyl-4,6-dinitrophenol of the formula OzN R where R has the same meanings as in Formula I.

In either of these methods, the reaction of the starting compound H or IV with phosgene, as well as the subsequent esterification of the intermediate IIa or IVa with the compound III or V, respectively, are preferably carried out in the presence of an inert organic solvent and in the presence of an acid-binding agent. Examples of suitable organic solvents are aromatic hydrocarbons, such as benezne, toluene or xylene, and ethers, such as tetrahydrofuran or dioxane. Examples of suitable acidbinding agents are alkali metal carbonates, alkali metal bicarbonates, alkali metal oxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkaline earth metal oxides, as well as organic bases, such as triethylamine, pyridine, N,N-dicyclohexyl-ethylamine and the like.

Also, in either of these methods, it is not necessary to isolate the intermediate chlorocarbonate IIa or IVa from the reaction mixture in which it is formed.

The starting compounds II and IV for methods A and B are known compounds.

The following examples further illustrate the preparation of compounds of the Formula I and will enable others skilled in the art to understand it more completely.

EXAMPLE 1 O- 2-sec.butyl-4,6-dinitro-phenyl -O'-( l-ethoxycarbonylethyl-1)-carbonate by method B A solution of 10.0 gm. (0.0416 mol) of 2-sec.butyl- 4,6-dinitro-phenol, 8.8 gm. (0.049 mol) of O-chloroformyl ethyl lactate (prepared by reacting ethyl lactate with phosgene) and 3.5 gm. (0.044 mol) of pyridine in 100 ml. of benzene was stirred at room temperature for several hours. Thereafter, the pyridine hydrochloride which had crystallized out was separated by vacuum filtration. The filtrate was extracted several times with anhydrous potassium carbonate to remove unreacted 2-sec. butyl-4,6-dinitro-phenol, and the extracts were discarded. The benzene was then distilled out of the extracted filtrate, initially at atmospheric pressure and toward the end in vacuo, leaving 14.9 gm. (93% of theory) of a yellowish oil, which was identified to be O-(2-sec.butyl-4,6-dinitrophenyl)-O-(l-ethoxycarbonyl-ethyl-l)-carbonate of the formula The product was thin-layer chromatographically uniform. Elemental Analysis.-Calculated (percent): C, 50.00; H, 5.24; N, 7.29. Found (percent): C, 49.81; H, 5.02; N, 7.36.

EXAMPLE 2 Using a procedure analogous to that described in Example 1, O (2 sec.butyl-4,6-dinitro-phenyl)-'-[1- ethoxy-carbonyl n propyl-(2)]-carbonate, a yellowish non-crystallizable oil, of the formula was prepared from O-chloroformyl ethyl-p-hydroxybutyrate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.-Calculated (percent): C, 51.3; H, 5.56; N, 7.04. Found (percent): C, 51.2; H, 5.47; N, 7.01.

EXAMPLE 3 Using a procedure analogous to that described in Example 1, O-(2 7 sec.butyl 4,6 dinitro-phenyl)-0'-[1- methoxy-carbonyl-ethyl]-carbonate, a yellowish noncrystallizable oil, of the formula H- C 1H5 OzN Ha NO:

was prepared from O-chloroformyl methyl lactate and 2- sec. butyl-4,6-dinitro-pheno1.

Elemental analysis.-Calculated (percent): C, 48.6; H, 4.89; N, 7.57. Found (percent): C, 48.5; H, 4.77; N, 7.51.

EXAMPLE 4 Using a procedure analogous to that described in Example l, O-( 2 s e :,butyl 4,6 digitro-phenyl)-O'-[1-iso- 4 propoxycarb onyl-ethyl] -carbonate, crystallizable oil, of the formula a yellowish non- OzN NO: CH3

was prepared from O-chloroformyl isopropyl lactate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.-Calculated (percent): 51.3; H, 5.56; N, 7.04. Found (percent): C, 51.0; H, 5.32; N, 6.89.

EXAMPLE 5 Using a procedure analogous to that described in Example 1, O-(2-sec.butyl 4,6 dinitro-phenyl)-O-[1-nbutoxycarbonyl-ethyl]-carbonate, a yellowish non-crystallizable oil, of the formula was prepared from O-chloroformyl n-butyl lactate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 52.5; H, 5.86; N, 6.80. Found (percent): C, 52.6; H, 5.89; N, 6.95.

EXAMPLE 6 Using a procedure analogous to that described in Example 1, O-(2-sec.butyl 4,6 dinitro-phenyl)-O-[1- n-amyloxycarbonyl-ethyl]-carbonate, a yellowish noncrystallizable oil, of the formula Using a procedure analogous to that described in Example 1, O-(2sec.butyl 4,6 dinitro-phenyl)-O-[1- isoamyl-oxycarbonyl-ethyl]-carbonate, a yellowish noncrystallizable oil, of the formula GEE-C2 5 OzN- N03 CH3 was prepared from O-chloroformyl isoamyl lactate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 53.6; 161,756.11; N, 6.58. Found (percent): C, 53.4; H, 5.90; N,

5 EXAMPLE 8 Using a procedure analogous to that described in Example 1, -(2-sec.bu-tyl 4,6 dinitro-phenyl)-O-[1- n-octyl-oxycarbonyl-ethyl]-carbonate, a yellowish noncrystallizable oil, of the formula N02 Ha was prepared from O-chloroformyl n-octyl lactate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 56.5; H, 6.90; N, 5.98. Found (percent): C, 56.2; H, 6.78; N, 6.06.

EXAMPLE 9 Using a procedure analogous to that described in Example 1, O-(2-sec.butyl 4,6 dinitro-phenyl)-O'-[1 methoxy-carbonyl-n-propyl 2)] carbonate, a yellowish non-crystallizable oil, of the formula was prepared from 9.0 gm. of O-chloroformyl methyl B-hydroxybutyrate and 10.0 gm. of 2-sec.butyl-4,6-dinitrophenol in the presence of 3.5 gm. of pyridine and 100 ml. of tetrahydrofuran. The yield was in excess of 80% of theory.

EXAMPLE Using a procedure analogous to that described in Example 1, 0-(2-sec.butyl 4,6 dinitro-phenyl)-O'-[1- isoamyl-oxycarbonyl-n-propyl (2)] carbonate, a yellowish non-crystallizable oil, of the formula H-OzHs OgN Using a procedure analogous to that described in Example 1, 0-(2-sec.butyl 4,6 dinitro-phenyl)-O'-['ln-dodecyl-oxycarbonyl-n-propyl (2)] carbonate, a yellowish non-crystallizable oil, of the formula OHa CHE-C2115 O2N NO: CH8

was prepared from O-chloroformyl n-dodecyl fl-hydroxybutyrate and 2-sec.buty1-4,6-dinitrophenol.

EXAMPLE 12 O- (2-sec.butyl-4, G-dinitro-phenyl) -O- l-ethoxycarbonyl-ethyD-carbonate 24.0 gm. (0.10 mol) of 2-sec.butyl-4,6-dinitro-phenol were dissolved in ml. of acetone, and then 5.56 gm. (0.0525 mol) of anhydrous sodium carbonate were added to the solution. The resulting mixture was boiled until the sodium carbonate had almost completely gone into solution (for about 30 minutes), and then the still undissolved sodium carbonate was filtered OE and the filter cake was washed with acetone. 19.0 gm. (0.105 mol) of O-chloroformyl ethyl lactate were added to the filtrate, and the resulting solution was refluxed for two hours. Thereafter, the sodium chloride which had separated out was isolated from the solution by centrifuging and vacuum-filtration and Washed with acetone. The wash liquid was combined with the filtrate, and the solution was evaporated until an oily residue was left. Finally, the oily residue was heated for 20 minutes at about 100 C. in a high vacuum to remove all residual volatile impurities. 37.7 gm. (98% of theory) of O-(2-sec.buty1-4,6-dinitrophenyl)-O'-(l-ethoxycarbonyl-ethyl)-carbonate were obtained.

EXAMPLE 13 O- 2- sec. amyl-4, G-dinitro-phenyl) -O- l-ethoxycarb onylethyl -carb onate A solution of 12.7 gm. (0.050 mol) of Z-sec-amyl- 4,6-dinitro-phenol, 10.8 gm. (0.060 mol) of O-chloroformyl ethyl lactate and 4.7 gm. (0.059 mol) of pyridine in 100 ml. of benzene was stirred for several hours at room temperature. Thereatfer, the pyridine hydrochloride which had crystallized out was separated by vacuumfiltration, and the filtrate was extracted several times with anhydrous potassium carbonate to remove unreacted 2- sec.amy1-4,6-dinitro-phenol. The filtrate was then diluted, initially at atmospheric pressure and toward the end in vacuo, to remove the benzene, leaving 19.1 gm. (96 of theory) of an oily residue which was identified to be 0- (2-sec.amyl-4,6-dinitro-phenyl)-O (l-ethoxycarbonylethyl)carbonate of the formula O J-OCHC O O CzHa N09 The product was thin-layer chromatographically uniform.

Elemental analysis.- Calculated (percent): C, 51.3; 'H, 5.56; N, 7.04. Found (percent): C, 51.1; H, 5.77; N, 6.86.

EXAMPLE 14 Using a procedure analogous to that described in Example 13, O-(2-methyl-4,6-dinitro-phenyl)-O'-[l-ethoxycarbonyl-ethyl1-carbonate, an oil, of the formula olN was prepared from O-chloroformyl ethyl lactate and 2- methyl-4,6-dinitro-phenol.

Elemental analysis-Calculated (percent): C, 45.60; H, 4.12; N, 8.18. Found (percent): C, 45.42; H, 4.25; N, 8.06.

7 EXAMPLE 15 Using a procedure analogous to that described in EX- ample 13, O-(2-methyl 4,6 dinitro-phenyl)-O-[1-nbutoxycarbonyl-ethyl]-carbonate, an oil, of the formula OzN- CH3 was prepared from O-chloroformyl n-butyl lactate and 2- methyl-4,6-dinitro-phenol.

Elemental analysis.'CalCulated (percent): C, 48.6; H, 4.90; N, 7.57. Found (percent): C, 48.54; H, 4.99; N, 7.51.

EXAMPLE 16 Using a procedure analogous to that described in Example l3, O-(2-isopropyl-4,6-dinitro-phenyl)-O'-[l-ethoxycarbonyl-ether]-carbonate, an oil, of the formula was prepared from O-chloroformyl ethyl lactate and 2- isopropyl-4,6-dinitro-phenol.

Elemental analysis.Calculatcd (percent): C, 48.60; H, 4.90; N, 7.57. Found (percent): C, 48.52; H, 4.84, N, 7.47.

EXAMPLE 17 Using a procedure analogous to that described in Example 13, O-(2-n-butyl-4,6-dinitro-phenyl)-O-[l-ethoxycarbonyl-ethyl]-carbonate, an oil, of the formula was prepared from O-chloroformyl ethyl lactate and 2-nbutyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 50.00; H, 5.24; N, 7.29. Found (percent): C, 49.79; H, 5.32; N, 7.18.

EXAMPLE 18 Using a procedure analogous to that described in Example 113, O (2 sec.amyl-4,6-dinitro-phenyl)-O-[lmethoxycarbonyl-ethyl]-carbonate, an oil, was prepared from O-chloroformyl methyl lactate and 2-sec.amyl-4,6- dinitro-phenol.

Elemental analysis.-Calculated (percent): C, 50.00; H, 5.24; N, 7.29. Found (percent): C, 49.75; H, 5.33; N, 7.01.

EXAMPLE 19 Using a procedure analogous to that described in Example 13, O (2 sec.amyl-4,6-dinitro-phenyl)-O'-[1- ethoxycarbonyl-ethyl] carbonate, an oil, was prepared from O-chloroformyl ethyl lactate and 2-sec.amyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 51.30; H, 5.56; N, 7.04. Found (percent): C, 51.10; H, 5.77; N, 6.86.

EXAMPLE 20 Using a procedure analogous to that described in Example 13, O (2-sec.amyl-4,6-dinitro-phenyl)-O'-[l-nbutoxycarbonyl ethyl]-carbonate, an oil, was prepared from O-chloroformyl n-butyl lactate and 2-sec.amyl-4,6- dinitro-phenol.

Elemental analysis.Calculated (percent): C, 53.60; H, 6.15; N, 6.58. Found (percent): C, 53.33; H, 6.20; N, 6.39.

EXAMPLE 21 Using a procedure analogous to that described in Example 13, O (2-sec.amyl-4,6-dinitro-phenyl)-O'-[l-n-octyloxycarbonyl-ethyl]-carbonate, and oil, was prepared from O-chloroformyl n-octyl lactate and 2-sec.amyl-4,6-dinitrophenol.

Elemental analysis.-Calculated (percent): C, 57.40; H, 7.11; N, 5.81. Found (percent): C, 57.06; H, 7.24; N, 5.60.

EXAMPLE 22 Using a procedure analogous to that described in Example 13, O (2-scc.amyl-4,6-dinitro-phenyl)-O-[l-ethoxycarbonyl-n-propyl-(2)]-carbonate, an oil, was prepared from O-chloroformyl ethyl fl-hydroxy-butyrate 2-sec.amyl- 4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 52.50; H, 5.85; N, 6.80. Found (percent): C, 52.21; H, 5.98; N, 6.52.

EXAMPLE 23 Using a procedure analogous to that described in Example 13, O (2-sec.octyl-4,6-dinitro-phenyl)-O-[l-ethoxycarbonyl-ethyl]-carbonate, a yellowish non-crystallizable oil, of the formula N02 Ha was prepared from O-chloroformyl ethyl lactate and 2- sec.octyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 54.50; H, 6.41; N, 6.37. Found (percent): C, 54.27; H, 6.43; N, 6.28.

EXAMPLE 24 Using a procedure analogous to that described in Example 13, O-(2-cyclohexyl-4,fi-dinitro-phenyl) -O'- l-ethoxycarbonyl-ethyl]-carbonate, an oil, of the formula OzN was prepared from O-chloroformyl ethyl lactate and 2- cyclohexyl-4,G-dinitro-phenol.

Elemental analy'sis. Calculated (percent): C, 52.70; H, 5.40; N, 6.84. Found (percent): C, 52.44; H, 5.49; N, 6.57.

The compounds embraced by Formula I above have useful properties. More particularly, they all exhibit very effective acaricidal activities, especially against red spider mites, while being non-toxic toward plants; a few of them also exhibit fungicidal, insecticidal and ovicidal activities.

For acaricidal purposes the compounds of the Formula I are applied as active ingredients in conventional liquid or sold pesticidal compositions, such as dusting powders, suspensions, emulsions, solutions, aerosols and the like. Such compositions may additionally comprise customary inert auxiliary ingredients, such as emulsifiers, diluents and adhesion-enhancing agents, as well as additional pesticidal agents. The effective acaricidal concentration range of the compounds of the Formula I in such compositions is from 0.001 to 5% by weight, based on the total weight of the composition.

The following examples illustrate a few acaricidal compositions comprising a compound of the Formula I as an active ingredient and represent the best modes contemplated of putting the invention into practical use.

The parts are parts by weight unless Otherwise specified.

EXAMPLE 25 Emulsion concentrate 20 parts of -(2-sec.butyl-4,6-dinitro-phenyl) -O' (1- ethoxycarbonyl-ethyl)-carbonate and 10 parts of butyl ricinoleate sulfonate were dissolved in 70 parts of a commercial mixture of aromatic hydrocarbons. The resulting concentrate was then emulsified in the required amount of water to make the concentration of the mixed carbonate in the aqueous emulsion about 0.02%. The emulsion was then sprayed at the rate of 2,000 liters/hectare on an apple orchard infested with red spider mites. A 100% kill of the spider mites was achieved Without injury to the apple trees. I

EXAMPLE 26 Wettable powder 20 parts of O-(2-sec.butyl-4,6-dinitro-phenyl)-0'-[1- methoXycarbonyl-n-propyl (2)] carbonate, 20 parts of kaolin, 5 parts of sodium sulfate, 2 parts of finely divided calcium carbonate, 8 parts of calcium lignin sulfonate, 2 parts of alkyl naphthalene sulfonate and 43 parts of siliceous chalk were intimately admixed with each other, and the mixture was milled. The resulting powder was suspended in a suflicient amount of water to make the concentration of the mixed carbonate in the aqueous suspension about 0.04%. The suspension was then sprayed at the rate of 2,000 liters/hectare on an apple orchard infested with red spider mites. A 100% kill of the spider mites was obtained without injury to the apple trees.

EXAMPLE 27 Dusting power 2 parts of O-(2-sec.butyl-4,6-dinitro-phenyl) -O'- [1- ethoxycarbonyl-ethyl]-carbonate were intimately admixed with 98 parts of kaolin, and the mixture was milled. The resulting powder was dusted at the rate of 30 kg./l1ectare on a bean field infested with red spider mites. A 100% kill of the spider mites was obtained without injury to the bean plants.

EXAMPLE 28 Wettable powder A mixture of 25 parts of O-(2-sec.amyl-4,6-dinitropheny1)-O-[l-ethoxycarbonylethyl] carbonate and 25 parts of diatomaceous earth Was thoroughly milled .with 2 parts of prepared chalk (calcium carbonate), 5 parts of anhydrous sodium sulfate, 33 parts of siliceous chalk, 9 parts of a stabilizer (Collex /s) and 1 part of a sodium alkylnaphthalenesulfonate wetting agent (Nekal BX78, GAF Corp). The resulting powder was suspended in a sufficient amount of water to make the concentration of the mixed carbonate in the aqueous suspension about 0.03%. The aqueous suspension was sprayed at the rate of 2,000 liters/hectare on an apple orchard infested with red spider mites. A 100% kill of the spider mites was obtained without injury to the apple trees.

EXAMPLE 29 Dusting powder A mixture of 2- parts of O-(2-sec.amyl-4,6-dinitrophenyl) O [l-ethoxycarbonyl-ethyl]-carbonate and 2 parts of diatomaceous earth was thoroughly admixed with 96 parts of kaolin, and the mixture was milled. The resulting powder was dusted at the rate of 20 kg./hectare on a bean field infested with red spider mites. A 100% kill of the spider mites was obtained without injury to the bean plants.

Analogous results were obtained when an equal amount of any one of the other compounds embraced by Formula I was substituted for the particular mixed carbonate in Examples 25 through 29. Likewise, the concentration of the active acaricidal ingredient in these examples may 10 be varied, as may the amounts and nature of the inert ingredients, to meet particular requirements.

While the present invention has been illustrated with the aid of certain specific embodiments thereof, it will be readily apparent to others skilled in the art that the invention is not limited to these particular embodiments, and that various changes and modifications may be made without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. An acaricidal composition consisting essentially of an inert solid or liquid carrier and an effective acaricidal amount of a compound of the formula a N Oz wherein R is straight or branched alkyl of 1 to 12 carbon atoms,

R is straight or branched alkyl of 1 to 8 carbon atoms or cyclohexyl, and

n is 0 or 1.

2. The composition of claim 1, wherein said compound is 0- 2-sec.butyl-4,6-dinitro-phenyl) -O'- l-ethoxycarbonyl-ethyl] -carbonate.

3. The composition of claim 1, wherein said compound is 0- (2-sec.butyl4,6-dinitro-phenyl) -O'- l-methoxy-carbonyl-n-propyl- (2) -carbonate.

4. The composition of claim 1, wherein said compound is O-(2-sec.amyl-4,6-dinitro-phenyl)-O-[1-ethoxycarbonyl-ethyl] -carbonate.

5. The method of killing acarids, which comprises contacting said acarids with an effective acaricidal amount of a compound of the formula CH3 N0 wherein R is straight or branched alkyl of 1 to 12 carbon atoms,

R is straight or branched alkyl of l to 8 carbon atoms or cyclohexyl, and

n is 0 or 1.

6. The method of claim 5, wherein said compound is O (2sec.butyl 4,6 dinitro-phenyl)-O"-[l-ethoxycarbonyl-ethyl]-carbonate.

7. The method of claim 5, wherein said compound is O-(2-sec.butyl 4,6 dinitro-phenyl)-O'-[l-methoxycarbonyl-n-propyl- (2) ]-carbonate.

8. The method of claim 5, wherein said compound is O-(2 sec.amyl-4,6-dinitro-phenyl)-O'-[l-ethoxycarbonyl-ethyl]-carbonate.v

References Cited UNITED STATES PATENTS 3,234,260 2/1966 Planka et al. 260463 3,419,620 12/1968 Becker et al 260-611 FOREIGN PATENTS 1,550,196 12/1968 France.

ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner UNI'I ED STATES PATENT OFFICE- CERTIFICATE OF CORRECTION Patent N0.'3,733,415 vDated May 15, 1973 InVEMOflS) liming-Manfred Bochor ot a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 12 insert Claims priority, applications Germany;

June '16, 1969 P 19 30 593. 2

December 5, 1969, P 19 61 210.3

Column 4, line 68, the formula should read as shown below:

Signed and sealed this 20th day of August 1974.

(SEAL) Attesc:

MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents USCOMM-DC 60376-P69 9 US. GOVERNMENT PRINTING OFFICE i969 0-356-334,

FORM PO-105O (10-69) 

